WO2021260275A1 - Method for processing black liquor soap - Google Patents
Method for processing black liquor soap Download PDFInfo
- Publication number
- WO2021260275A1 WO2021260275A1 PCT/FI2021/050495 FI2021050495W WO2021260275A1 WO 2021260275 A1 WO2021260275 A1 WO 2021260275A1 FI 2021050495 W FI2021050495 W FI 2021050495W WO 2021260275 A1 WO2021260275 A1 WO 2021260275A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- fraction
- resin
- resin acids
- organic solvent
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000000344 soap Substances 0.000 title claims abstract description 50
- 238000012545 processing Methods 0.000 title abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 99
- 150000007513 acids Chemical class 0.000 claims abstract description 67
- 239000011347 resin Chemical class 0.000 claims abstract description 65
- 229920005989 resin Chemical class 0.000 claims abstract description 65
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 43
- 239000000194 fatty acid Substances 0.000 claims abstract description 43
- 229930195729 fatty acid Natural products 0.000 claims abstract description 43
- 238000005886 esterification reaction Methods 0.000 claims abstract description 31
- 230000032050 esterification Effects 0.000 claims abstract description 26
- -1 fatty acid esters Chemical class 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 24
- 150000004665 fatty acids Chemical class 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000003784 tall oil Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 13
- 229930182558 Sterol Natural products 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 11
- 239000008346 aqueous phase Substances 0.000 claims description 11
- 238000005191 phase separation Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 150000003432 sterols Chemical class 0.000 claims description 11
- 235000003702 sterols Nutrition 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 8
- 235000011149 sulphuric acid Nutrition 0.000 claims description 8
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 7
- 239000011122 softwood Substances 0.000 claims description 7
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 239000000061 acid fraction Substances 0.000 claims description 5
- 238000011534 incubation Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000011949 solid catalyst Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000012223 aqueous fraction Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000000605 extraction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 12
- 238000004821 distillation Methods 0.000 description 10
- 235000019439 ethyl acetate Nutrition 0.000 description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000000526 short-path distillation Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- SBJKKFFYIZUCET-JLAZNSOCSA-N Dehydro-L-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(=O)C1=O SBJKKFFYIZUCET-JLAZNSOCSA-N 0.000 description 2
- KRHAHEQEKNJCSD-UHFFFAOYSA-N Dihydroasparagusic acid Natural products OC(=O)C(CS)CS KRHAHEQEKNJCSD-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- LGJMUZUPVCAVPU-UHFFFAOYSA-N beta-Sitostanol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(CC)C(C)C)C1(C)CC2 LGJMUZUPVCAVPU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 238000004185 countercurrent chromatography Methods 0.000 description 2
- JYGAZEJXUVDYHI-UHFFFAOYSA-N dihydroartemisininic acid Natural products C1CC(C)=CC2C(C(C)C(O)=O)CCC(C)C21 JYGAZEJXUVDYHI-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000002038 ethyl acetate fraction Substances 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 238000003818 flash chromatography Methods 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 238000004810 partition chromatography Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical class [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 1
- KZJWDPNRJALLNS-VPUBHVLGSA-N (-)-beta-Sitosterol Natural products O[C@@H]1CC=2[C@@](C)([C@@H]3[C@H]([C@H]4[C@@](C)([C@H]([C@H](CC[C@@H](C(C)C)CC)C)CC4)CC3)CC=2)CC1 KZJWDPNRJALLNS-VPUBHVLGSA-N 0.000 description 1
- CSVWWLUMXNHWSU-UHFFFAOYSA-N (22E)-(24xi)-24-ethyl-5alpha-cholest-22-en-3beta-ol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(CC)C(C)C)C1(C)CC2 CSVWWLUMXNHWSU-UHFFFAOYSA-N 0.000 description 1
- VGSSUFQMXBFFTM-UHFFFAOYSA-N (24R)-24-ethyl-5alpha-cholestane-3beta,5,6beta-triol Natural products C1C(O)C2(O)CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(CC)C(C)C)C1(C)CC2 VGSSUFQMXBFFTM-UHFFFAOYSA-N 0.000 description 1
- KLEXDBGYSOIREE-UHFFFAOYSA-N 24xi-n-propylcholesterol Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(CCC)C(C)C)C1(C)CC2 KLEXDBGYSOIREE-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- 240000000940 Araucaria angustifolia Species 0.000 description 1
- 235000018719 Araucaria angustifolia Nutrition 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LPZCCMIISIBREI-MTFRKTCUSA-N Citrostadienol Natural products CC=C(CC[C@@H](C)[C@H]1CC[C@H]2C3=CC[C@H]4[C@H](C)[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C)C(C)C LPZCCMIISIBREI-MTFRKTCUSA-N 0.000 description 1
- ARVGMISWLZPBCH-UHFFFAOYSA-N Dehydro-beta-sitosterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)CCC(CC)C(C)C)CCC33)C)C3=CC=C21 ARVGMISWLZPBCH-UHFFFAOYSA-N 0.000 description 1
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 1
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 description 1
- 235000014466 Douglas bleu Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000014556 Juniperus scopulorum Nutrition 0.000 description 1
- 235000014560 Juniperus virginiana var silicicola Nutrition 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 241000218595 Picea sitchensis Species 0.000 description 1
- 241000218606 Pinus contorta Species 0.000 description 1
- 235000005018 Pinus echinata Nutrition 0.000 description 1
- 241001236219 Pinus echinata Species 0.000 description 1
- 235000011334 Pinus elliottii Nutrition 0.000 description 1
- 235000017339 Pinus palustris Nutrition 0.000 description 1
- 240000007320 Pinus strobus Species 0.000 description 1
- 235000008578 Pinus strobus Nutrition 0.000 description 1
- 235000008582 Pinus sylvestris Nutrition 0.000 description 1
- 241000218626 Pinus sylvestris Species 0.000 description 1
- 235000008566 Pinus taeda Nutrition 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 240000001416 Pseudotsuga menziesii Species 0.000 description 1
- 235000005386 Pseudotsuga menziesii var menziesii Nutrition 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 235000008691 Sabina virginiana Nutrition 0.000 description 1
- LGJMUZUPVCAVPU-JFBKYFIKSA-N Sitostanol Natural products O[C@@H]1C[C@H]2[C@@](C)([C@@H]3[C@@H]([C@H]4[C@@](C)([C@@H]([C@@H](CC[C@H](C(C)C)CC)C)CC4)CC3)CC2)CC1 LGJMUZUPVCAVPU-JFBKYFIKSA-N 0.000 description 1
- 241000202349 Taxus brevifolia Species 0.000 description 1
- 241000218638 Thuja plicata Species 0.000 description 1
- 240000003021 Tsuga heterophylla Species 0.000 description 1
- 235000008554 Tsuga heterophylla Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- MJVXAPPOFPTTCA-UHFFFAOYSA-N beta-Sistosterol Natural products CCC(CCC(C)C1CCC2C3CC=C4C(C)C(O)CCC4(C)C3CCC12C)C(C)C MJVXAPPOFPTTCA-UHFFFAOYSA-N 0.000 description 1
- NJKOMDUNNDKEAI-UHFFFAOYSA-N beta-sitosterol Natural products CCC(CCC(C)C1CCC2(C)C3CC=C4CC(O)CCC4C3CCC12C)C(C)C NJKOMDUNNDKEAI-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 229940107161 cholesterol Drugs 0.000 description 1
- 230000001906 cholesterol absorption Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 description 1
- 229940118781 dehydroabietic acid Drugs 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000014684 lodgepole pine Nutrition 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- 125000004492 methyl ester group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
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- NFBAXHOPROOJAW-UHFFFAOYSA-N phenindione Chemical compound O=C1C2=CC=CC=C2C(=O)C1C1=CC=CC=C1 NFBAXHOPROOJAW-UHFFFAOYSA-N 0.000 description 1
- 229960000280 phenindione Drugs 0.000 description 1
- 229940068065 phytosterols Drugs 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000012521 purified sample Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000001520 savin Nutrition 0.000 description 1
- 235000000673 shore pine Nutrition 0.000 description 1
- KZJWDPNRJALLNS-VJSFXXLFSA-N sitosterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CC[C@@H](CC)C(C)C)[C@@]1(C)CC2 KZJWDPNRJALLNS-VJSFXXLFSA-N 0.000 description 1
- 235000015500 sitosterol Nutrition 0.000 description 1
- 229950005143 sitosterol Drugs 0.000 description 1
- NLQLSVXGSXCXFE-UHFFFAOYSA-N sitosterol Natural products CC=C(/CCC(C)C1CC2C3=CCC4C(C)C(O)CCC4(C)C3CCC2(C)C1)C(C)C NLQLSVXGSXCXFE-UHFFFAOYSA-N 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- LGJMUZUPVCAVPU-HRJGVYIJSA-N stigmastanol Chemical compound C([C@@H]1CC2)[C@@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@H](C)CC[C@@H](CC)C(C)C)[C@@]2(C)CC1 LGJMUZUPVCAVPU-HRJGVYIJSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
- C11B13/02—Recovery of fats, fatty oils or fatty acids from waste materials from soap stock
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
- C11B13/005—Recovery of fats, fatty oils or fatty acids from waste materials of residues of the fabrication of wood-cellulose (in particular tall-oil)
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
Definitions
- the present invention relates to a method for processing black liquor soap, espe cially to a method for producing and recovering fatty acid esters.
- Black liquor soap is a by-product of the industrial sulphate cellulose production process.
- Tall oil soap is a by-product of the industrial sulphate cellulose production process of soft wood.
- Such soap is processed by sulphuric acid treatment, which converts the ionic forms of resin acids and fatty acids into the acid form producing tall oil.
- tall oil soap is a by-product, which is basically completely converted to tall oil by sulphuric acid treatment.
- tall oil soap contains several valuable chemical compounds and fractions which have commercial value. This potential is unused in the current process.
- Tall oil soap is produced when fatty acids and resin acids of the wood material are converted into ionic forms in the alkaline conditions. Once the alkaline solution is evaporated, the tall oil soap concentrates on the top of the solution, where it can be collected mechanically. This fraction is then treated with sulphuric acid and the tall oil is formed as a viscose fraction. Tall oil is further distilled to produce fatty acid and resin acid fractions.
- WO 2018/065876 A1 discloses a process for separating unsaponifiables from tall oil soap (TOS) using co-distillation.
- WO 2017/130127 A1 discloses an extraction of phytosterols from alkaline tall oil soap which is obtained from the Kraft process black liquor by skimming.
- Turhanen etal. (ACS omega 2019; 4, 8974 -8984) discloses esterification reactions using carboxylic acids and alcohols as a starting material using a cation exchange resin catalyst.
- the present disclosure generally relates to methods for processing black liquor soap.
- the aspect of the invention is a method for producing and recovering fatty acid es- ters and resin acids. Characteristic steps of said method are depicted in claim 1.
- the method provides a catalytic selective esterification and fractionation process for black liquor soap. Compared to prior art processes the method is environmentally friendly and economic.
- the present invention provides a method for producing fatty acid esters using an acid catalyst (e.g. mineral acid catalyst, such as H2SO4, organic acids, such as trifluoroacetic acid (TFA), or acid form solid catalyst, such as ion exchange resin catalyst) and recovering them from black liquour soap.
- an acid catalyst e.g. mineral acid catalyst, such as H2SO4, organic acids, such as trifluoroacetic acid (TFA), or acid form solid catalyst, such as ion exchange resin catalyst
- Especially the present invention provides a method for producing fatty acid esters and separating them from resin acids of tall oil soap with an acid catalyst.
- the inventors have suprisingly found that dissolving black liquor soap to alcohol enables a direct selective esterification of fatty acids. Alcohol serves as a solvent and as a substrate for the reaction.
- the acid catalyst enhances the esterification process and improves selectivity towards primary carboxyl acids.
- One advantage of the invention is the use of a selective catalyst in the esterification reaction of the fatty acids within the soap. This is an environmentally friendly and more efficient way than a traditional sulphuric acid treatment.
- the fatty acid esters and resin acids obtainable by the method here disclosed are environmentally friendly “green label” products when compared to raw oil based products.
- An advantage of the present invention is improved energy and cost efficiency in black liquor soap processing. Distillation of high boiling point products, such as fatty acids or resin acids, may be avoided, greatly enhancing the energy efficiency of the process. Furthermore, the separation of fatty acids (as esters) from resin acids is achieved through the selective esterification in a simple, low-cost process. Black liquor soap may be processed with more energy-efficient methods. Using the method of the present invention, the product fractions obtained from the black liquor soap may be separated and purified by simple extraction and precipitation steps, without the need of distillation of the product fractions themselves. Only low boiling point solvents are recycled via evaporation or distillation techniques.
- a further advantage of the present invention is the industrial scalability and compat ibility of the method with existing industrial processes. No vast modifications of al ready existing black liquor processing sites are needed.
- the invention provides pre extractions and raw compounds that can directly be used in existing processes and processing sites.
- a yet further advantage of the present invention is that the method enables recycling of the used solvents.
- Alcohols and organic solvents used in the method are partly or entirely recyclable through evaporation and distillation methods, making the pre sent invention compatible with the concept of circular economy.
- Figure 1 shows 1 H NMR spectrum measured from black liquor soap used as a start ing material.
- Figure 2 shows 1 H NMR spectrum measured from separated fraction containing mixture of fatty acids methyl esters obtained from resin-catalysed esterification.
- Figure 3 shows 1 H NMR spectrum measured from separated fraction containing mixture of resin acids obtained from resin-catalysed esterification.
- Figure 4 shows 1 H NMR spectrum measured from pure DHAA (>97%) fraction sep arated by High Performance Counter Current Chromatography (HPCCC) from mix ture of resin acids obtained from resin-catalysed esterification.
- HPCCC High Performance Counter Current Chromatography
- Figure 5 shows 1 H NMR spectrum measured from mixture of resin acids obtained from resin-catalysed esterification, in which the DHAA has been separated by HPCCC.
- Figure 6 shows 1 H NMR spectra measured from mixture of resin acids in residual sample and purified resin acids obtained from acid-catalysed esterification.
- the present invention provides a method for producing and recovering fatty acid esters from black liquor soap.
- the method comprises the steps of a. dissolving black liquor soap to alcohol; and b. adjusting pH to ⁇ 8, preferably ⁇ 7 with acid; and c. adding either a catalyst or a strong acid to obtain selective esterification; and d. incubating under mixing to allow at least partial esterification of fatty acids of the soap; and e. separating the alcohol and recovering the remaining fraction comprising fatty acid esters; and f. adding alkali to the recovered fraction; and g. extracting the product with an organic solvent to collect the fatty acid esters to the separated organic solvent; and h. recovering resin acids from an aqueous phase remaining after step g.
- the black liquor soap may be a soap produced within pulping of softwood, preferably the soap is a tall oil soap.
- Recovering of the resin acids in step h. may be carried out by extraction or precipitation methods or phase separation using chemical additives, for example.
- the alcohol in step a. may be any alcohol able to form esters with fatty acids. It may be cyclic alcohol, aromatic alcohol, sugar containing alcohol, branched alcohol or alcohol with straight chain. Typically alcohols with high molecular weight require more harsh reaction conditions, a stronger, i.e., more effective catalyst, elevated temperature and/or prolonged reaction time. Optimization of these parameters can be done by a person skilled in the art. Common industrial or research grade alcohols are suitable for the present invention. Typically, the weight percentage of the used alcohol may be in the range of 70-100 wt-%, preferably 80-95 wt-% of the total weight of the solvent, the remainder typically being water and/or other impurities.
- suitable alcohols are C1-5 alcohols such as methanol, ethanol, butanol. propanol, isopropanol, preferably methanol or ethanol. In one embodiement the alcohol is methanol. Alcohol as a solvent is also a substrate for the esterification reaction.
- the volume ratio of the alcohol to the black liquor soap may be in the range of 1 :2 - 10:1 (volume of alcohol : volume of black liquor soap), preferably 1 :1 - 8:1 , more preferably 2:1 - 5:1 .
- the acid at steps b. and/or c. may be any strong acid, which typically have a pKa value less than 4, such as mineral acid, such as nitric acid (HNO3), hydrochloric acid (HCI), perchloric acid (HCIO 4 ) or sulphuric acid (H 2 SO 4 ), or organic acid, such as trifluoroacetic acid or formic acid.
- mineral acid such as nitric acid (HNO3), hydrochloric acid (HCI), perchloric acid (HCIO 4 ) or sulphuric acid (H 2 SO 4 ), or organic acid, such as trifluoroacetic acid or formic acid.
- HNO3 nitric acid
- HHI3 hydrochloric acid
- HIO 4 perchloric acid
- sulphuric acid H 2 SO 4
- organic acid such as trifluoroacetic acid or formic acid.
- the acid is H 2 SO 4 commonly used within pulp & paper industry.
- a selective esterification may be accomplished by carefully selecting the pH of the reaction mixture in step c.
- the selective esterification is obtained by adding either a catalyst or a strong acid in step c.
- the pH value is ⁇ 0.
- the pH value may be in the range of -2.5 - 0, preferably -1 - 0.
- the fatty acid esterification reaction is incomplete, and fatty acids may transfer to the resin acids fraction.
- the fatty acid content of the resin acids fraction may be up to 25 mol-% of the resin acids fraction.
- the inventors have surprisingly found that by selecting the pH value to be ⁇ 0, the fatty acids may selectively be esterified and a fatty acid content in the resin acids fraction may be less than 10 mol-%, such as 0- 10 mol-%, preferably less than 5 mol-%, such as 0-5 mol-% of the resin acids fraction.
- the selective esterification of fatty acids may be obtained by using a catalyst together with the acid.
- the catalyst may be added to the reaction mixture after the acidifying step b.
- pH values may be higher than when using acid only.
- pH value may be ⁇ 8, preferably ⁇ 7.
- the pH value may be in the range of -2 - 8, preferably 0 - 7, more preferably 1 - 5, or even more preferably 1 - 4.
- the catalyst may be any catalytic compound causing esterification, usually an acid form solid catalyst, such as an ion exchange resin catalyst, preferably a cation exchange catalyst.
- Non-limiting examples of commercial catalyst are Dowex 50WX8, Dowex Marathon C, Amberlite, Amberjet IRC, C, Diaion, Indion, Purolite and Purofine.
- the resin catalyst used in the process is recyclable.
- the acid form solid catalyst may be recovered for re-use by known methods such as filtration or centrifugation after the incubation in step d.
- step d. may be further enhanced by adding a dried Nal catalyst in connection of step c.
- the incubation at step d. is performed at a temperature below the boiling point of the used alcohol, e.g. at a temperature of 10 to 80 °C. Typical incubation times at ambient temperature are 8 to 48 hours and at ambient temperature or temperatures 40, 60 or 80 °C for 2 to 36 hours. Alcohols with longer or more hindered carbon chain length, such as isopropyl alcohol, may require elevated temperatures.
- Separation of the alcohol in step e. may be done by evaporation in vacuo or e.g. using distillation methods including short path distillation to recycle most of the alcohol.
- the evaporation of alcohol may be done to dryness.
- the alkali added in step f. may be any earth alkali hydroxide, such as KOH or NaOH, preferably NaOH. It is added until pH is at least 7, such as at least 8, 9, 10, 11 or 12. Typically pH is at least 10.
- the pH value may be in the range of 7-14, such as 8-14, 9-14, 10-14, 11-14, or 12-14. Typically the pH value is in the range of IQ- 14.
- the alkali is typically added as a solution having a concentration of 1-10 M. The aim is to make the solution basic so that resin acids are totally water soluble (in salt form) and not extractable to an organic solvent. Thus, resin acid salts can then be recovered from the aqueous phase.
- Water may be added into the recovered fraction with the alkali in step f.
- the volume of water added may be approximately the same as the volume of black liquor soap originally used.
- the volume ratio of the water added in step f. to the volume of black liquor soap originally used may be in the range of 1 :2— 2: 1 , preferably 2:3- 3:2.
- the fatty acid esters are recovered in step g.
- the recovery is carried out by extracting the product obtained in step f. with an organic solvent to collect the fatty acid esters to the separated organic solvent.
- the organic solvent in step g. may be any water insoluble organic solvent capable to extract the produced fatty acid esters or resin acids from the water phase, such as ethyl acetate, dichloromethane (DCM), hexane, pentane, heptane, cyclohexane, toluene, chloroform, preferably ethyl acetate being easily recycled within the process, non-toxic, environmentally friendly and easy to use.
- the organic solvent used in the process is recyclable.
- step f. The basic mixture obtained in step f. is typically extracted 2 times in step g.
- the volume ratio of the organic solvent to the volume of the black liquor soap originally used may be in the range of 1 :2 — 4: 1 , preferably 2:3 -3:1 , more preferably 1 :1 - 2:1.
- the fatty acid esters are separated from the organic solvent by evaporating the organic solvent.
- Evaporation of the organic solvent may be done by evaporation in vacuo or e.g. using distillation methods, such as short path distillation to recycle most of the organic solvent.
- the evaporation of the organic solvent may be done to dryness.
- the fatty acid esters remain after the solvent evaporation in step g. as a thick liquid.
- the resin acids are recovered in step h. from an aqueous phase remaining after step g.
- the resin acids recovery may be carried out by e.g. extraction or phase separation methods.
- the resin acids may be recovered by extraction using the following further steps hi . acidifying the remaining aqueous phase with mineral acid; and h2. extracting with organic solvent; and h3. evaporating said organic solvent to recover a resin acids fraction to provide the resin acids fraction.
- the resin acids extraction may alternatively comprise the following further steps hi . acidifying the remaining aqueous phase with mineral acid; and h2. extracting with organic solvent; and h3. adding alkali until phase separation is completed; and h4. separating the resin acid fraction for further purification.
- the organic solvent in step h2. may be any water insoluble organic solvent capable to extract the produced fatty acid esters or resin acids from the water phase, such as ethyl acetate, dichloromethane (DCM), hexane, pentane, heptane, cyclohexane, toluene, chloroform, preferably ethyl acetate being easily recycled within the process, non-toxic, environmentally friendly and easy to use.
- the organic solvent used in the process is recyclable.
- Evaporation of the organic solvent may be done by evaporation in vacuo or e.g. using distillation methods, such as short path distillation to recycle most of the organic solvent.
- the resin acids may then be easily collected and possibly further purified.
- the alkali may be added in step h. to enhance the phase separation of the resin acids from the organic solvent.
- the alkali added in step h. may be any earth alkali hydroxide, such as KOH or NaOH, preferably NaOH. It is added until pH is at least 7, such as at least 8, 9, 10, 11 or 12. Typically pH is at least 10.
- the pH value may be in the range of 7-14, such as 8-14, 9-14, 10-14, 11-14, or 12-14. Typically the pH value is in the range of 10-14.
- the alkali is typically added as a solution having a concentration of 1-10 M. Salts of organic acids, such as the resin acids, are not soluble in organic solvents.
- the resin acids convert to their respective salts upon the alkali addition, and thus become insoluble in the organic solvent.
- the phase separation is enhanced, and the resin acids may be easily collected for further purification.
- the organic solvent may be collected after the phase separation and recycled for further use.
- the resin acids may be recovered by separation using the following further steps hi . acidifying the remaining aqueous phase with acid, providing deionized resin acids as a phase on top of the aqueous fraction; and h2. collecting the resin acid fraction.
- the resin acids may easily be collected from the surface of the aqueous fraction. This is due to the fact that resin acids are insoluble to water in their acid form.
- Acidification under step hi in both extraction and phase separation methods converts resin acid salts to respective acids.
- mineral acids remain in the aqueous phase and thereby enhance recovery and reuse of the organic phase.
- the acidification may be carried out using mineral acids, such as HCI, H 2 SO 4 , or trifluoroacetic acid, or mixtures thereof, preferably H 2 SO 4 .
- the pH value is typically adjusted to ⁇ 7, preferably ⁇ 4, such as in the range of -2 - 7, 0 - 5, or 1 - 4 in order to efficiently convert the resin acid salts to the deionized form.
- the resin acids may be further separated and purified by industrial-scale chromatographic methods, such as liquid-liquid extraction chromatography, preferably high-performance counter current cromatography (HPCCC) or centrifugal partition chromatography (CPC).
- industrial-scale chromatographic methods such as liquid-liquid extraction chromatography, preferably high-performance counter current cromatography (HPCCC) or centrifugal partition chromatography (CPC).
- HPCCC high-performance counter current cromatography
- CPC centrifugal partition chromatography
- stanols and/or sterols may be separated and recovered from the black liquor soap.
- Stanols and/or sterols contained in the black liquor soap may precipitate during the esterification process in step d.
- the precipitate comprising stanols and/or sterols, such as sitostanol and sitosterol, may be separated from the product obtained in step d of the method.
- Stanols and/or sterols may be recovered by methods known in the art, such as filtering from the product obtained in step d.
- the stanols and/or sterols obtained from the black liquor soap may be further separated and purified by flash-chromatography (FLASH) using solvents and solid phases known in the art.
- flash-chromatography FLASH
- liquid-liquid extraction chromatography techniques such as high performance counter current chromatography (HPCCC) or centrifugal partition chromatography (CPC) may be used.
- HPLC high performance liquid chromatography
- stanols and sterols may be separated as a profitable by-product by simple and cost-efficient process steps.
- the resulting stanols and/or sterols may be used, e.g., as dietary supplements due to their cholesterol-lowering effects.
- Plant stanols and/or sterols are known to block choles terol absorption sites in the human intestine, thus helping to reduce cholesterol ab sorption in humans.
- Tall oil soap (ca. 55 g) obtained from typical Nordic Kraft process for soft wood was dissolved in MeOH (200 ml) and pH adjusted with cone. H 2 SO 4 to ⁇ 0. The mixture was allowed to react at room temperature for 18 h under stirring.
- MeOH was evaporated and ca. 100 ml water was added to the residue.
- Example 3 Acid-catalysed esterification and resin acid phase separation using chemical additives EtOAc fraction (1500 ml) obtained from 500 g of black liquor soap after similar pro cess as described in the Example 3 was made alkaline with a suitable base, e.g. NaOH or KOH or Mg(OH)2 until phase separation is completed. Typically 99 mol-% separation is achieved as indicated by NMR spectra of separated phases.
- EtOAc fraction 1500 ml obtained from 500 g of black liquor soap after similar pro cess as described in the Example 3 was made alkaline with a suitable base, e.g. NaOH or KOH or Mg(OH)2 until phase separation is completed. Typically 99 mol-% separation is achieved as indicated by NMR spectra of separated phases.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
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US18/010,943 US20230235245A1 (en) | 2020-06-26 | 2021-06-24 | Method for processing black liquor soap |
CA3186595A CA3186595A1 (en) | 2020-06-26 | 2021-06-24 | Method for processing black liquor soap |
EP21829622.6A EP4172296A4 (en) | 2020-06-26 | 2021-06-24 | Method for processing black liquor soap |
BR112022026624A BR112022026624A2 (en) | 2020-06-26 | 2021-06-24 | METHOD FOR PROCESSING BLACK LIQUEUR SOAP |
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FI20205682A FI129803B (en) | 2020-06-26 | 2020-06-26 | Method for processing black liquor soap |
FI20205682 | 2020-06-26 |
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PCT/FI2021/050495 WO2021260275A1 (en) | 2020-06-26 | 2021-06-24 | Method for processing black liquor soap |
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US (1) | US20230235245A1 (en) |
EP (1) | EP4172296A4 (en) |
BR (1) | BR112022026624A2 (en) |
CA (1) | CA3186595A1 (en) |
FI (1) | FI129803B (en) |
WO (1) | WO2021260275A1 (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2640823A (en) * | 1946-06-04 | 1953-06-02 | Pittsburgh Plate Glass Co | Treatment of tall oil |
US7540889B2 (en) * | 2006-07-11 | 2009-06-02 | Bluekey Energy Inc. | Production of a refinery feedstock from soaps produced during a chemical pulping process |
CN102181323A (en) * | 2011-03-29 | 2011-09-14 | 南京林业大学 | Method for preparing biodiesel |
CN103184064A (en) * | 2013-04-10 | 2013-07-03 | 南京林业大学 | Method for preparing biodiesel based on crude sulphate soap as material |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1736802A (en) * | 1926-10-11 | 1929-11-26 | Schultze Willi | Process of treating talloel |
US2348970A (en) * | 1942-04-07 | 1944-05-16 | Continental Res Corp | Process for the separation of acids contained in tall oil |
US2395284A (en) * | 1942-08-01 | 1946-02-19 | Lovas Joseph John | Process of separating and recovering constituents of waste liquor from the soda and sulphate processing of coniferous woods |
US2573890A (en) * | 1948-09-04 | 1951-11-06 | Pittsburgh Plate Glass Co | Separation of tall oil components |
-
2020
- 2020-06-26 FI FI20205682A patent/FI129803B/en active IP Right Grant
-
2021
- 2021-06-24 CA CA3186595A patent/CA3186595A1/en active Pending
- 2021-06-24 WO PCT/FI2021/050495 patent/WO2021260275A1/en unknown
- 2021-06-24 EP EP21829622.6A patent/EP4172296A4/en active Pending
- 2021-06-24 BR BR112022026624A patent/BR112022026624A2/en unknown
- 2021-06-24 US US18/010,943 patent/US20230235245A1/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US2640823A (en) * | 1946-06-04 | 1953-06-02 | Pittsburgh Plate Glass Co | Treatment of tall oil |
US7540889B2 (en) * | 2006-07-11 | 2009-06-02 | Bluekey Energy Inc. | Production of a refinery feedstock from soaps produced during a chemical pulping process |
CN102181323A (en) * | 2011-03-29 | 2011-09-14 | 南京林业大学 | Method for preparing biodiesel |
CN103184064A (en) * | 2013-04-10 | 2013-07-03 | 南京林业大学 | Method for preparing biodiesel based on crude sulphate soap as material |
Non-Patent Citations (2)
Title |
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See also references of EP4172296A4 * |
TURHANEN PETRI A., LEPPÄNEN JUKKA, VEPSÄLÄINEN JOUKO J.: "Green and Efficient Esterification Method Using Dried Dowex H + /NaI Approach", ACS OMEGA, ACS PUBLICATIONS, US, vol. 4, no. 5, 31 May 2019 (2019-05-31), US , pages 8974 - 8984, XP055894666, ISSN: 2470-1343, DOI: 10.1021/acsomega.9b00790 * |
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EP4172296A4 (en) | 2024-07-10 |
US20230235245A1 (en) | 2023-07-27 |
BR112022026624A2 (en) | 2023-01-24 |
FI129803B (en) | 2022-08-31 |
EP4172296A1 (en) | 2023-05-03 |
CA3186595A1 (en) | 2021-12-30 |
FI20205682A1 (en) | 2021-12-27 |
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